Process for the manufacture of cyanogen formarylides



Patented July 7, 1931 UNITED STATES PATENT OFFICE JOHANNES PFLEGER, 0F FRANKFORT-ON-THE-MAIN, GERMANY, ASSIGNOR T'O DEUTSCHE GOLD &JSILBER SOHEIDEANSTALT VORMALS ROLESSLER, OF FRANKFORT- ON-THE-MAIN, GERMANY, A CORPORATION PROCESS FOR THE MANUFACTURE OF CYANOGEN FORMARYLIDES No Drawing. Application filed February 14, 1929, Serial No. 340,018, and in Germany November'20, 1928.

The invention relates to a process for the manufacture of cyanogen formarylides 1n which the nitrogen is substituted by radicals, groups or the like and which have the general formula It is known that acid cyanides of the formula RCOCN can be produced by reacting acid chlorides upon HCN in the presence of pyridine when the reaction is carried out in ether solution. It was, however, impossible hitherto to cause this reaction with formic acid chlorides of the formula Under the given conditions these chlorides either did not react at all or only to a small extent or they turned into resinous matter so that, in consequence, the yield as regards nitriles was only a very small one.

I have made now the surprising observation that the above mentioned chlorides may be made to react with hydrocyanic acid at ordinary temperature with formation of cyanogen formarylides the nitrogen of which is substituted and, generally, with very good yield if they are brought together in the presence of pyridine but in the absence of diluting agents which do not take part in-the reaction. Polymerization of the hydrocyanic acid did not occur to any appreciable extent nor were any other polymerization products formed. In some cases it was beneficial to slightly raise the temperature.

In the formula '-45 or non-substituted, aromatic or aliphatic group. The latter group may be linked to the other group forming a ring therewith.

' Ewample I 184 parts N-ethyl-aniline-formic chloride are dissolved in 400 parts of pyridine. 35 parts hydrocyanic acid are added to the solution. The vessel is then sealed hermetically and heated during 8 hours to to 60 centigrade. The pyridine is separated from the reacting product by evaporation in vacuo.

The residue is digested in the cold with dilute- Eazample ll 85 parts methyl-analine-formic chloride are mixed with 50 parts by volume of pyridine and 22 parts by volume of hydrocyanic acid and the mixture is heated-to to centi-grade for 2 to 3 hours in a pressure vessel. When cold the mass is taken up in ether, the so-lution washed with dilute hydrochloric acid then with soda, dried and after evaporation of the solvent distilled in vacuo. 60 parts by Weight of cyanogen formmethylanilide distill overbetween 154 and 156 centigrade at 15 mm, pressure. The distilled 'mass solidifies in crystals. Fusion point 64 to 65 centigrades. Yield 75%.

According to my invention I am able to produce a great number of substances amongst which I enumerate the ,following which are colourless and furnish -well de-' lined crystals.

The following are formulas of such substances prepared in each case from the starting material given, by way of forming the intermediate acid chlorides by the method of Michler (B-erichte der Deutschen Chemischen Gesellschaft, Bd. 9, p. 399, und Bd. 12, p. 1165) which may be represented, for eX- ample, by the following equation:

from phenylglycine nitrile:

OHzCN oooN Fusion p0int=143 Cen. crystallized from methanol,

from p-bromo methylaniline:

Fusion point= Cen. crystall. from methanol Bil from py-tetrahydroquinoline:

| COCN Fusion point=74 Cen, crystall. from methanol,

from dihydro-a-methyl-indol:

Fuslon Point: 78 Cen. crystall. from methanol OOCN from diphenylamine Fusion point=132 Cen. crystalli GOCN from methanol from 8 ethyl-l-naphthylamine H502 HN-OOCN Fusion p0int=6l Cen. crystall. from methanol from ethyl-Q-naptylamine:

I Fusion point=l04 Cen. N from ethylalcohol OOCN from py-tetrahydro-B-naphthoquinoline:

4? a. bg/ O l l Fusion point=134 Cen.

/ O CJ from ethylaleohol What I claim is:

1. A process for the manufacture of nitrogen substituted cyanogen formarylides of the general formula wherein Ar is any substituted or unsubstituted aromatic residue and R is any substituted or substituted aromatic or alphatic residue, which consists in'reacting the corresponding acid chlorides of the general formula:

with hydrocyanic acid in pyridine in the absence of any diluting agents other than pyridine. a

2. A process for the manufacture of nitrogen substituted cyanogen forinarylides of the general formula:

wherein Ar is any substituted or unsubstituted aromatic residue and R is any substituted or unsubstituted aromatic or aliphatic residue, which consists in heating the corre sponding acid chlorides of the general formula: 

